In infrared ("IR") spectroscopy a beam of light from an infrared source is passed through a sample. The light that is transmitted through the sample is evaluated in comparison with the incident light and its intensity plotted as a function of wavelength or wavenumber. Wavenumber is expressed herein as centimeters.sup.-1 or "cm.sup.-1 ". This spectral plot or spectrum can provide information regarding the functional groups and structural features of the sample and, accordingly, IR spectroscopy has become a valuable tool in analytical chemistry for certain types of samples.
The infrared region of the electromagnetic spectrum extends from the upper end of the visible region (wavenumber of approximately 14,300 cm.sup.-1) to the microwave region (near 20 cm.sup.-1). The region which is typically of most interest to analytical chemists for determination of structural features of an organic sample is from about 4000 cm.sup.-1 to about 400 cm.sup.-1. In this region of the spectrum, organic compounds absorb incident infrared light at frequencies corresponding to the vibrational frequencies of the compound. These absorbed frequencies are characteristic of the structural features of the compound or compounds in the sample and can permit rapid identification. The intensities of the peaks in the spectral plot or spectrum are a function of the concentration of the sample, extinction coefficient, and path length of the incident light through the sample.
To obtain an infrared spectrum of a sample, the sample is typically applied to a sample holder or "cell". This sample holder or cell holds the sample in the path of the incident beam of infrared light. It is essential that the material used for the sample holder be highly transmissive in that region of the IR spectrum which is of interest. Also, the sample holder should not be soluble in, or reactive with, either the sample or solvent (if any). Illustrative examples of materials used in sample holders include inorganic salts, glasses, and quartz.
Sodium chloride (NaCl) is perhaps the most commonly used material since it does not absorb infrared light in the range of 4000 to 625 cm.sup.-1 and is relatively less expensive than some alternatives. However, NaCl crystals are very susceptible to moisture and easily broken. For a discussion of cell materials see Pasto and Johnson, Organic Structure Determination, Prentice-Hall, Inc., 1969, pp. 145-147.
In the majority of analyses, the holder (or cell) is a pair of plates made from crystals of an inorganic salt that has been precisely machined and polished for maximum optical clarity. A sample is then placed between the pair of plates and mounted by a variety of techniques in the beam of infrared light. Solid samples are often ground and intimately mixed with an inorganic salt such as potassium bromide, pressed into a thin wafer or pellet, applied to a sample holder, and mounted in the infrared beam. Alternatively, samples may be mulled with an oil such as NUJOL.TM. mineral oil, applied to a sample holder, and analyzed as a thin film. Liquid samples, either neat or in solvent, may also be analyzed using a sealed cell in which a pair of plates are sealed together with a spacer to provide a chamber in which the sample is held. In addition to the use of plates, other sample preparation techniques have been developed. For instance, liquids or solutions having a relatively high surface tension such as aqueous solutions have been analyzed by suspending a thin film from a loop of wire. Also, a solution may be coated and dried to form a film, e.g., a solution may be coated on a film of polytetrafluoroethylene and dried, and the resulting thin film peeled from the polytetrafluoroethylene and analyzed.
Due to the susceptibility of many known cell materials to degradation by moisture and the long drying time necessary for preparation of some samples, analysis of aqueous samples is difficult. Increasingly stringent regulations have prompted many industries to reduce or eliminate organic solvent use and emissions, prompting the development of water-based processes and products. Illustrative examples of materials that have been used for cells for use with aqueous samples include silver bromide, calcium fluoride, and barium fluoride. Use of such materials is limited by the typically high expense, limited useful spectral ranges, burdensome maintenance, and difficult sample preparation associated with such materials. Typically, aqueous samples are analyzed using a horizontal attenuated total reflectance ("ATR") crystal to which a sample is applied. A beam of infrared light is reflected repeatedly through the sample before being evaluated in a detector. Use of this technique is hampered by the high cost of sample holders and difficulties encountered in sample preparation and maintenance. In part due to these problems, IR spectroscopy has not reached its potential as a routine tool for analysis of aqueous samples.
In addition to the problems described, namely cost, sensitivity to moisture and fragility, commercially available cells have high maintenance requirements. In view of the high costs, disposal of these cells is prohibitive. Accordingly, sample holders must be carefully cleaned, typically with organic solvents, after each analysis to prevent contamination from one sample to the next. In some instances, the solvents may present health risks to operators. In addition, the high cost of sample holders tends to inhibit retention of samples on a long term basis.
Dove and Hallett, Chemistry and Industry, 1966, pp. 2051-53, describe an all-plastic evacuable cell to be used for infrared or ultraviolet spectroscopic analysis of gases. The cell has windows that can be made from RIGIDEX.TM. Type 35 polyethylene. The relative thickness of the windows, i.e., about 3 millimeters, would preclude the use of such sample holders in most routine IR spectroscopic analysis due to the strong absorbances. Andrede, J.Chem. Ed., 66(10), p. 865, 1989, describes using polyethylene film as windows in a sample cell. For sampling of liquids the author suggests applying the sample to a film stretched over a ring, covering the sample with a second film, and securing both stretched films with a second ring.
IR spectroscopy has been used as a tool in the analysis of polymer films. Osland, Laboratory Practice, 37(2), p. 73, 1988, describes a heated press used to prepare plastic films for analysis by IR. Love and Wool, A.C.S. Polymeric Material Science and Engineering, analyzes semi-crystalline polymer films by Fourier Transform Infrared Spectroscopy (FTIR). Benson, European Plastics News, p. 26, 1989, describes using IR radiation to measure the thickness or gauge of polymer films.
Owen and Wood, J.Chem. Ed., 64(11), 1987, pp. 976-79, describe the use of tissue paper as a support matrix to obtain infrared spectra of solids and non-volatile liquids. This method would appear to be impractical due to the fragility of the paper and the strong interfering absorbances of the cellulose. As a result, the signal-to-noise ratio or sensitivity is quite low.
Jackson, "Novel Sampling and Support Media for the Infrared Analysis of Water-immiscible Oil-based Environmental Pollutants", Analyst, vol. 109, March 1984, pp. 401-02, discloses the use of stretched polytetrafluoroethylene tapes as a support medium for recovery and infrared spectroscopic analysis of water-immiscible organic pollutants.
U.S. Pat. No. 4,942,297 (Johnson et al.) discloses an apparatus for collection and infrared spectroscopic analysis of aerosol-borne particulates.
Thus, there is a need for a commercially available sample cell that is inexpensive, easy to use, insensitive to or non-reactive with liquids such as water or organic solvents, and has a useful spectral range for most routine analysis.